A new way for heterogeneous nucleation of crystals from the solution is described: 3D crystalline structure can nucleate and grow encompassing gaseous cavities, formed on solid substrates in the aqueous solution, so giving rise to crystal bubbles. The double surface of a crystal bubble is made, in this case, by the faces of the cleavage calcite rhombohedron separating the solution from the enclosed gas cavity. The faces thickness and the edges length amount to a few nanometers and to about 5 Pin, respectively. Then, the surface-to-volume ratio is the highest obtained for 3D crystals, amidst the consulted literature. Bubbles' shape is explained through the equilibrium properties of crystal-cavity and crystal-solution interfaces and in terms of growth mechanisms operating on the separate interfaces. The nucleation of the crystals around gas cavities can provide new insight on those mineralization phenomena where the gas phase participate in crystal growth. Potential applications are also envisaged concerning the nucleation of the gas cavities on peculiar templates which impose I D (or 213) periodicity to crystal bubbles, in order to obtain I D and/or 2D photonic crystals. (C) 2002 Elsevier Science B.V. All rights reserved.